Alpha,alpha-di-(fluoroalkyl)benzylamines and their preparation from aromatic compounds and fluoroalkylideneimines



United States Patent U.S. Cl. 260570.8 7 Claims ABSTRACT OF THE DISCLOSURE a t-Di(fluoroalkyl)benzylamines, e.g., 4,4'-OXyb'lS[0z,otbis(trifluoromethyl)benzylamine], and their preparation from aromatic compounds and fluoroalkylideneimines, e.g., diphenyl ether and hexafluoroisoproylideneimine. The compounds are useful as precursors of polyamides.

Related application This application is a continuation-in-part of my copending application Ser. No. 445,968, filed May 14, 1965, and now abandoned.

Description of the invention This invention relates to a t-(ii(fluoroalkyDbenzylamines and to their preparation.

The new compositions of this invention are the class of benzylamines having the formula wherein Y is fluorine, chlorine or a 1-6 carbon perfluoroalkyl, w-chloroperfiuoroalkyl or w-hydroperfluoroalkyl radical and Y is defined as R or is hydrogen with the proviso that, when Y is hydrogen, Y is fluorine or l-6 perfiuoroalkyl; n is an integer from 1-2; and Q is the radical formed by removal of 11 hydrogen atoms from a compound HQH selected from the group consisting of monocyclic, polycyclic, and fused polycyclic compounds containing 1-3 siX-membered carbocyclic aromatic rings, and polycyclic compounds containing two six-membered carbocyclic aromatic rings which are joined through a bridge selected from the group consisting of O,

and tCH l where R is selected from the group consisting of hydrogen, phenyl and alkyl of 1-6 carbon atoms, and m is an integer from 16; with the proviso that each said carbocyclic aromatic ring contains 04 substituents selected from the group consisting of alkyl, perfiuoroalkyl, hydroxy, alkoxy, phenoxy, alkylthio, amino, monoalkylamino, dialkylamino, cyclopentyl, cyclohexyl, halo and nitro, with each of said alkyl and alkoxy moieties containing l-6 carbon atoms.

The compounds of this invention are prepared by reacting, in the presence of a Friedel-Crafts catalyst, a compound HQH with a polyfiuoroalkylideneimine of the general formula Y CF -C(=NH)CF Y The symbols Q, Y and Y have the same definitions as provided above.

The imines employed herein as reactants are obtained by reacting a polyfiuoroketone with at least one molar equivalent of ammonia at 50 to 10 C., followed by dehydration of the resulting aminohydroxy polyfluoroalkane with a dehydrating agent in the presence of an acid acceptor, and then distilling to recover the imine. The imine reactant also may be prepared by reacting hydrazoic acid with a polyfluorothioketone. Both of the aforesaid preparatory methods for the polyfiuo-roalkylideneimine :are disclosed and claimed in U.S. Pat. 3,226,439.

The second reactant in the preparatory process of the present invention is an aromatic compound HQH which contains at least one aromatic ring capable of entering into Friedel-Crafts condensation reactions with alkyl halides in the presence of aluminum chloride. More particularly, in the compound HQH, Q is the radical remaining after removal of one or two hydrogen atoms therefrom and may be an aryl or arylene radical of one to three siX-membered carbocyclic aromatic rings, thus providing a total of six to eighteen carbon atoms in the aromatic system, or Q may be an atom-interrupted aryl or arylene radical in which two siX-membered carbocyclic aromatic rings are separated by a divalent group X, the latter being O, S-,

wherein R is hydrogen, phenyl or alkyl of 1 to 6 carbon atoms and m is 1 to 6. Moreover, each carbocyclic ring in the radical Q may, but need not, have substituents in addition to those already described above. Thus, each carbocyclic ring may contain 1 to 4 substituents selected from the group consisting of alkyl, perfiuoroalkyl, hydroxy, alkoxy, phenoxy, alkythio, amino, monoalkylamino, di'alkylamino, cyclopentyl, cyclo'hexyl, halo and nitro, with each of said alkyl and alkoXy moieties containing 1 to 6 carbon atoms. Examples of HQH compounds useful for preparing the benzylamines of this invention are benzene, naphthalene, anthracene, phenanthrene, toluene, the Xylenes, ethyl-, propyl-, butyl-, or n-hexylbenzene, methyl naphthalene, cyclohexylbenzene, l-methyl-3-butylbenzene, diphenyl, dibenzyl, the mono-, dior tetrafluorobenzenes, benzotrifluoride, monochlorobenzene, l-methyl 3 bromobenzene, ortho-dichlorobenzene, phenol, 1-hydroXy-4-hexylbenzene, 1,4-dihydroxybenzene, methoxybenzene, butoxybenzene, 1-methy1-4- ethoxybenzene, 1,3,5-trimethylbenZene, aniline, ll-Ilaphthylamine, N-butylaniline, N,N-dimethylaniline, N,N-diethyltoluidine, 4-nitrodiphenyl, diphenyl ether, methyl naphthyl ether, diphenylamine, triphenylamine, N-ethyl dihpenylamine, diphenyl thioe'ther, methyl phenyl thioether, and the like.

The aromatic compound employed must contain at least one ring capable of reacting with the fiuoroalkylideneimine. As indicated above, this reactivity is readily determined by testing whether or not the aromatic compound undergoes the convention Friedel-Crafts condensation reaction with an alkyl halide in the presence of aluminum chloride. Whether or not the reaction can lead to a product containing 1 to 2 aminodi(fiuoroalkyl)methyi groups is determined primarily by the presence or absence on the aromatic ring or rings of substituents which either activate or inhibit the Friedel-Crafts reaction, and secondarily, by the mole ratio of alkylideneimine to HQH compound charged to the reactor. The two reactants can be used in any desired molar ratio, but usually between 0.25 and 5 moles of imine per mole of aromatic reactant. When the mole ratio of imine to HQH is 1:1 or less, the principal product is a monoamine. When the ratio of imine to HQH is at least 2:1 on a molar basis, then substantial amounts of the diamine generally are formed.

In general, the reaction between the HQH compound and the alkylideneimine is carried out in the presence of a Friedel-Cratts catalyst, such as aluminum chloride, aluminum bromide, boron trichloride, boron trifluoride, antimony pentachloride, zinc chloride, ferric chloride, hydrogen fluoride, stannic chloride, and the like.

The amount of catalyst used can be as low as 0.005% by weight of the imine. However, amounts up to the molar equivalent of the imine can be used and in cases where the product has a high tendency to complex with the Friedel-Crafts catalyst, the use of such amounts constitutes the preferred practice.

The reaction between the HQH compound and alkylideneimine can be efiected in the presence or absence of an organic liquid reaction medium which is unreactive with the reactants and reaction product under the conditions of reaction. Suitable media are the normally liquid aliphatic and cycloaliphatic hydrocarbons, such as the hexanes, heptanes, octanes, cyclohexanes, methylcyclohexane, and other inert solvents, such as tetrachloroethane, tetrachloroethylene, carbon disulfide, and the like. Usually, however, the HQH compound is employed in amounts such that it functions both as a reactant and reaction medium.

The temperature at which the reaction between the HQH compound and alkylideneimine is conducted depends upon such variables as the reactivity of the HQH compound and the nature of the Friedel-Crafts catalyst used. With very active HQH compounds and catalysts, reaction can take place at temperatures as low as C. The upper temperature is determined solely by the stability of the reactants and the reaction product. Most generally, the reaction is carried out at temperatures in the range of 50 to 300 C., preferably in the range of 100 to 275 C. Conveniently, the reaction is conducted in sealed reactors under autogenous pressure. This, however, is not a necessary condition and other types of reactors can be used.

The examples which follow are provided to illustrate but not limit the present invention. The reactor lining referred to in the examples as Hastelloy is a nickel-ironmolybdenum alloy. Representative polyfluoroalkylideneimines used as starting materials in the process of this invention are prepared as described in the following examples A, B, C and D.

EXAMPLE A Pyridine (500 ml.) contained in a 1-liter flask fitted with a condenser cooled with solid carbon dioxide, a mechanical stirrer, thermometer and a gas inlet tube, was cooled to 25 C. by means of a solid carbon dioxide-acetone bath. The stirrer was started, and 200 g. (1.2 moles) of hexafiuoroacetone was distilled into the flask, keeping the temperature between 25 and 30 C. Ammonia, 25 ml. at 78 C. (ca. 20.4 g., 1.2 moles), was then distilled into the stirred reaction mixture, keeping the temperature between 25 and 30 C. The cooling bath was replaced with a heating mantle, and the reaction mixture was warmed to 25 C. the condenser was replaced with a water-cooled condenser connected to a trap cooled with solid carbon dioxide, and 100 ml. (184 g., 1.2 moles) of phosphorus oxychloride was added dropwise at such a rate that gentle reflux was maintained. The gas that escaped through the condenser was collected in the cold trap. After the addition was completed (ca. 30 min.), the reaction mixture was heated to 100 C. and held there for 30 minutes. The condensate in the trap was distilled through a 40 cm.-packed column to give 138 g. (70% yield) of hexafiuoroisopropylideneimine as a colorless liquid, B.P. 1616.5 C., M.P. 47 C., d 1.51; IR 5.98p. for C=N. The P NMR spectrum showed two quartets centered at +5.77 and +7.62 p.p.m. (I =6 c.p.s.) of equal area, with the lower field quartet further split to a doublet (J =2.5 c.p.s.). The proton NMR spectrum showed a single broad band at 11.8 p.p.m.

An y is-C lled. for C HF N: C., 21.83; H, 0.61; F,

4 69.07; N, 8.46. Found: C, 21.81; H, 0.76; F, 68.81; N, 8.16.

EXAMPLE B A solution of 171 g. (100 ml. at 78 C., 0.937 mole) of chloropentafluoroacetone in 500 ml. of pyridine was cooled to -30 C. and 20 m1. (about 0.94 mole) of ammonia at 78 C. was slowly distilled thereinto. The mixture was then allowed to warm to room temperature and 100 ml. of phosphorus oxychloride was added dropwise over a period of 30 minutes. An exothermic reaction ensued and the temperature of the reaction mixture rose to C., as refluxing began. The lower boiling material was removed from the reaction mixture by distillation, and the fraction that boiled below C. was redistilled through a spinning band column. There was obtained 102 g. (60%) of chloropentafluoroisopropylideneimine as a colorless liquid, B.P. 4647 C. (mostly 46.7), 11 1.3130. The infrared spectrum contained a band at 5.92 4 for C=N. The P NMR spectrum showed evidence of two isomeric forms of this imine. The predominant isomer showed a quartet (I -:7 c.p.s.) for CF at +4.34 p.p.m. further split to a doublet (J =2 c.p.s.), and a higher field triplet (J =7 c.p.s.) for CF at +2.83 p.p.m. further split to a doublet (J =2.3 c.p.s.). The isomer present in lesser amount showed a quadruplet (J =7 c.p.s.) for CF further split to a doublet (1:1.8 c.p.s.) at -2.08 p.p.m. and a triplet (I =7 c.p.s.) for CE, at +5.05 p.p.m. The proton NMR showed a broad singlet centered at +11.6 p.p.m.

Analysis.-Calcd. for C HClF N: C, 19.86; H, 0.56; Cl, 19.55; F, 52.34; N, 7.77. Found: C, 20.24; H, 0.75; Cl, 19.64; F, 51.95; N 7.65.

EXAMPLE C A mixture of 100 ml. of dry pyridine and 75 g. (0.28 mole) of decafiuorodiethyl ketone (40 ml. at -78 C.) was kept below -25 C. and stirred while 6 ml. of ammonia was added. The mixture was then warmed to room temperature, and 24 ml. of phosphorus oxychloride was added dropwise at a rate sufficient to maintain gentle reflux. Volatile material was distilled into an ice-methanol trap (pot to 100 C.) and redistilled giving 9.4 g. (13%) of starting ketone and 271 g. (42% yield) of decafluoro-3- pentylideneimine, B.P. 52 C., n 1.3227. IR showed an NH band at 304 i and a C N band at 5.99,u.. The proton NMR exhibited a single peak at +122 p.p.m. and the P NMR showed multiplets at +149 (area 3), +15.6 (area 3), +486 (area 2) and +519 (area 2) p.p.m. (internal FCCl reference).

Analysis.Calcd. for C HF N: C, 22.65; H, 0.38; F, 71.41; N, 5.29; M.W. 265. Found: C, 23.06; H, 0.64; F, 71.65; N, 5.50; 265 (mass spec.).

EXAMPLE D Pentafluoroisopropylideneimine is prepared according to the following sequence of reactions:

NH2 Preparation of N-phenylpentafiuoroisopropylideneimine A mixture of 71.4 g. (0.6 mole) of phenylisocyanate, 92 g. (0.62 mole) of pentafluoroacetone and 10 g. of triphenylphosphine oxide was heated at 200 C. for 16 hours in a 400-ml. bomb. The bomb was cooled and vented, and the contents were distilled to give 75.6 g. (56% yield) of N-phenylpentafiuoroisopropylideneimine as a light yellow oil, B.P. 596-60 C. (10 mm), 11 1.4394. The

F NMR (internal FCCl reference) spectrum indicated a mixture of two isomers (syn and anti). The major isomer (82%) showed a triplet (1 :7) to doublet (1 :1.3) at 69.3 p.p.m. and a doublet (J :52) to quartet (J :7) centered at 120.4 p.p.m. The minor isomer (18%) showed a triplet (J :7) to doublet (1 :13) at 62.1 p.p.m. and a doublet (1 :52) to a quartet (1:13) at 125.4 p.p.m. The H NMR spectrum of the major isomer showed a multiplet (H) centered at 13.00 and a triplet (1 :52) to a quartet (1:1.3) centered at 73.96 (1H); and the minor isomer showed a multiplet at 77.0 (5H) and a triplet (1:52) centered at 13.84 (1H). The ultraviolet spectrum showed 327 my (e=15,500)

The infrared spectrum had an absorption at 5.88 1 for Anzilysz's.-Calcd. for C H F N: c, 48.44; H, 2.71; F, 42.57; N, 6.28. Found: C, 48.77; H, 2.92; F, 42.51; N, 6.27.

Preparation of pentafiuoroisopropylideneimine Ammonia, 21 ml. at 78 C. (ca. 1 mole) was slowly distilled into 74.3 g. (0.33 mole) of N-phenylpentafluoroisopropylideneimine contained in a flask cooled by an ice bath and connected to a Dry Ice-cooled condenser. The reaction mixture was allowed to reflux for 2 hours, and then stirred at room temperature overnight. The entire reaction mixture, ca. 60 ml., was mixed with 200 g. of phosphorus pentoxide contained in a flask connected to a simple still. The flask was heated strongly to distill out the volatile products. The distillate was redistilled to give 26.1 g. (52% yield) of pentafluoroisopropylideneimine as a colorless liquid, B.P. 4 .5 C., n 13. This imine was also prepared in 38% yield by a pyrolytic distillation at atmospheric pressure of N-phenylpentafiuoroisopropylideneimine.

The P NMR (internal FCCI reference) spectrum indicated the presence of two isomers (syn and anti). The major isomer (58%) showed a triplet (1:45) to a doublet (1:2.4) centered at 71.8 p.p.m. (3F) and a doublet (1:54 c.p.s.) to quartets (1:4.5 c.p.s.) to doublets (1:4.5) centered at 127.0 p.p.m. (2F); the minor isomer (42%) showed a triplet (1:6) to triplet (1:1) at 72.6 p.p.m. and a doublet (1:53) to quartets (1:6) to doublets (1:3.4) centered at 123.4 p.p.m. The H NMR spectrum of the mixture of isomers showed a broad absorption at 1:1.66 for NH, with the CH of the major isomer as a triplet (1:54) to a doublet (1:0.5) centered at 13.80 and the CH of the minor isomer as a triplet (1:53) to quartets (1:1.0) to doublets (1:1.0) centered at 13.69. The infrared spectrum of the isomeric mixture indicated a C=N at 5.87;, NH at 3.0311, and CH at 3.32;.

Analysis.Calcd. for C H F N: C, 24.49; H, 1.37; F, 64.60; N, 9.53. Found: C, 24.80; H, 1.52; F, 64.78; N, 9.42.

EXAMPLE 1 or. a)zC=NH Q-on mN-hQ-on A 21-gram sample (0.125 mole) of hexafluoroisopropylideneimine was added to a 240 ml. Hastelloy-lined autoclave containing 1 g. of aluminum chloride and 21 g. (0.219 mole) of phenol. The mixture was heated at 150 C. for 8 hr., cooled to room temperature and vented. The recovered semisolid (32 g.) was mixed with ether and filtered to remove undissolved salts. The ether solution (ca. 100 ml.) was dried over magnesium sulfate, concentrated under aspirator pressure and distilled. After ether and excess phenol were removed, 15.6 g. (50%) of 4-hydroxy-u,a-bis(trifluoromethyl)benzylamine, B.P. 80 C. (1.0 mm.), M.P. 70-73 C., was obtained. The

infrared spectrum of this material was consistent with the assigned structure. The ultraviolet spectrum showed max.

Example 1 was repeated using 22 g. of imine, 21 g. of phenol and 1 g. of hydrogen fluoride instead of aluminum chloride at 150 C. for 8 hr. to yield 22.6 g. of 4-hydroxy-a,o-bis(trifluoromethyl)benzylamine.

EXAMPLE 3 Example 1 was repeated substituting 4 g. of boron trifluoride for aluminum chloride to give about a 40% yield of the same benzylamine.

EXAMPLE 4 Using the reaction and work-up procedure described in Example 1, 31.5 g. of slightly impure 4-methoxy-a,abis(trifluoromethyl)benzylamine, B.P. 65 C. (1.2 mm.), was obtained from 40 g. of hexafluoroisopropylideneimine, 22 g. of anisole and 3.36 g. of aluminum chloride at 150 C. for 8 hr. A sample was purified by preparative gas chromatography and exhibited a M.P. of 5353.5 C. The H NMR of the benzylamine contained a sharp singlet at 7: 6.24 (-OOH a broad peak at :7.8 (NH and an A B pattern centered at 7:2.8 (paradisubstituted aromatic); the F NMR shows a singlet at +4219 c.p.s. from internal fluorotrichloromethane at 56.4 mc.

Analysis.-Calcd. for C 'I-I ONF (273.18): C, 43.96; H, 3.32; N, 5.13; F, 41.73. Found: C, 43.84; H, 3.53; N,

omno=nn @4111.

I CF3 A 17.4 gram sample of 4-methyl-a,u-bis (trifluoromethy1)benzylamine (B.P. C./ 100 mm.) was prepared by heating 25 g. of toluene, 3.12 g. of aluminum chloride and 25 g. of hexafluoroisopropylideneimine at C. for 8 hr. using the reaction and work-up procedure of Example 1. The ultra-violet spectrum of this benzylamine showed maxima at 268 (6 114), 265 (e: 196), 259 (5:243), 252 (e:199) and 210 III/l. (e:8.340) which is characteristic of a p-disubstituted benzene. The H NMR had an A B pattern at 1:26 (aromatic) a singlet at 1:7.83 (CH and at 7:795 (NH,,) and the F NMR was a singlet at +4202 c.p.s. from internal fluorotrichloromethane at 56.4 me.

Analysis.-Calcd. for C H NF (257.18): C, 46.69; H, 3.53; N, 5.45; F, 44.33. Found: C, 46.56; H, 3.61; N, 5.48; F, 44.10.

3,5-dimethyl-4-hydroxy oc,ot bis (trifiuoromethy1)benzylamine (8 g., M.P. 65 68 C.) was prepared from 25 g. of 2,6-dimethylphenol, 25 g. of hexafluoroisopropylideneimine and 1 g. of hydrogen fluoride at 150 C. for 8 hr. as described in Example 1. The amine was isolated by short path distillation, at 0.3 mm., of a 25 g. sample of the crude reaction mixture (42 g. was the total recovered). The P NMR showed a singlet at +4228 c.p.s. from int. FCCl at 56.4 mc.; and the H NMR contained singlets at 'r=7-7 (CH 2.6 (arom. H) and a very broad peak at =7 NH OH).

EXAMPLE 7 4 phenyl a,ot-bis(trifluorornethyl)benzylamine, 4 g., B.P. 135 C. (2 mm.), M.P. 9396 C., was prepared from 33 g. of hexafiuoroisopropylideneimine, 3.06 g. of aluminum chloride and g. of biphenyl at 150 C. for 8 hr. as described in Example 1. The amine was isolated by short path distillation of 21 g. sample of the reaction mixture (39 g. was the total recovered). The ultraviolet spectrum showed k 252 m (e=19,000); the P NMR showed a singlet at +4158 c.p.s. from int. FCCl at 56.4 mo. and the H NMR exhibited an -NH absorption at r=8.0 and aromatic absorptions at 7:25 with the proper ratio.

Analysis.Calcd. for C H F N (319.25): C, 56.43; H, 3.48; N, 4.34; F, 35.72. Found: C, 55.64; H, 3.48; N, 4.36; F, 36.49.

a,a-bis(trifluoromethyl)benzylamine, 4.6 g., B.P. 95 C. (60 mm.) was prepared from g. of benzene, 25 g. of hexafluoroisopropylideneimine and 4.0 g. of aluminum chloride at 200 C. for 8 hr., as per Example 1. The ultraviolet spectrum showed:

which is characteristic of a mono-substituted benzene. The H NMR showed an --NH peak at 1-=7.9 and aromatic absorption at 1:23 in the proper intensities.

Analysis.-Calcd. for C9H7NF6 (243.16): C, 44.46; H, 2.90; N, 5.76; F, 46.89. Found: C, 44.75; H, 2.72; N, 5.54; F, 46.54.

EXAMPLE 9 4 phenyl agar-bis(trifluoromethyl)benzylamine, 40 g. crude, was prepared from 40 g. of hexafiuoroisopropylideneimine, 15 g. of biphenyl and 3.2 g. of aluminum chloride at 175 C. for 16 hr. as per Example 1. Characterizalion is given in Example 7.

8 EXAMPLE 10A A 34 g. sample of hexafluoroisopropylideneimine was added to 3.22 g. of aluminum chloride and .24 g. of N,N- dimethylaniline at 78 C. in an autoclave and the mixture was heated at 150 C. for 8 hr. as described in Example 1. A black solid, 52 g., was recovered from the autoclave. This material was dissolved in ether and filtered to remove a green solid. The blue filtrate was evaporated to dryness and then taken up in pentane and filtered to remove a blue solid. The yellow filtrate was concentrated and cooled in an ice bath to yield, after filtration, a white solid, 14.7 g., M.P. 58.559.5 C. A second crop, 6.5 g., was also recovered. This white solid was 4-N,N-dimethylamino 8,04 bis(trifiuoromethyl) benzylamine. The ultraviolet spectrum showed: A 292 (6 24-00), 262 (e=21,000). The P NMR gave a singlet at +4185 c.p.s. from internal FCCl at 56.4 me. and the H NMR showed the characteristic A 8 pattern at 7:2.9, CH absorption at 7:7.16 and an NH band at =8.05, all with the proper intensities.

AIIHZYSI Sc-CfilCd. for cnH gNzFe C, H, 4.23; N, 9.81; F, 39.83. Found: C, 46.94; H, 4.50; N, 9.45; F, 40.01.

EXAMPLE 10B A mixture of 6.06 g. (0.05 mole) of N,N-dimethylaniline, 0.75 g. of aluminum chloride, and 7.35 g. (0.05 mole) of pentafluoroisopropylideneimine was stirred at 25 C. for 20 hours, and then heated at 100 C. for 4 hours. The entire reaction mixture was distilled at reduced pressure. After removal of unchanged imine and aniline, 4 dimethylamino a trifluoromethyl a-difiuoromethylbenzylamine was obtained as a liquid, B.P. -80 C. (1 mm.), that solidified to a glass upon cooling. The benzylamine was characterized by its H and P NMR spectra. The H spectrum in (CD CO showed a singlet (6H) at 16.86 for N(CH a broad absorption (2H) at 16.40 for NH and a triplet (1 =54 c.p.s.) centered at 73.23 (1H) for CF H in addition to absorption due to aromatic H. The F spectrum showed a triplet (1:8.5 c.p.s.) at 74.0 p.p.rn. for CE; and a doublet (1:54 c.p.s.) split further to a quartet (1:8.5 c.p.s.) centered at 130.1 p.p.m. (internal FCCl reference) for CF H.

EXAMPLE 1 1 CFa 4-amino-a,a-bis(trifluoromethyl)benzylamine, 2.15 g., M.P. 69-70 C., was obtained from 19 g. of aniline, 3 g. of hydrogen fluoride and 33 g. of hexafiuoroisopropylideneimine by heating at 150 C. for 8 hours using the reaction procedure of Example 1. The product was isolated by distillation of the recovered liquid (54 g.) and recrystallization (from pentane-ether) of the fraction boiling at 81 C./4.5 mm.85 C./5 mm. The ultraviolet spectrum, X 287 (5:1700), 247 m (E=13,150), was characteristic of p-substituted anilines. The H NMR had the characteristic A 13 pattern centered at r:2.9 and a broad peak at r:7.l for the NE -absorptions and the F EXAMPLE 12 4 N,N dimethylamino a,u bis(trifluoromethyl)- benzylamine, 11 g., was prepared as per Example 10A from 24 g. of N,N-dimethylaniline, 33 g. of hexafluoroisopropylideneimine and 3 g. of hydrogen fluoride by heating at 150 C. for 8 hours.

EXAMPLE 13 4-rnethyl-ot,a-bis(trifiuoromethyl)benzylamine, 55.6 g., was prepared as per Example 5, from 100 g. of toluene, 3 g. of aluminum chloride and 100 g. of hexafluoroisopropylideneimine by heating at 150 C. for 8 hours except that the reaction mixture recovered from the autoclave was worked up by filtering and then distilling the filtrate.

4-chloro 05,0: bis(trifiuoromethyl)benzylamine, 0.3 g., B.P. 50 C. (1.25 mm.), Was prepared from 22 g. of chlorobenzene, 3 g. of aluminum chloride and 34 g. of hexafluoroisopropylideneimine using the reaction procedure of Example 1. The product was isolated by filtering the reaction mixture (30 g.) and then distilling the filtrate. The H NMR had the characteristic A B pattern centered at 7:7.85 and the P NMR showed a singlet at +4204 c.p.s. from int. FCCl at 56.4 mc.

Analysis.Calcd. for C H NF CI (277.63): C, 39.94; H, 2.18; N, 5.05; F, 41.07; Cl, 12.77. Found: C, 39.40; H, 2.63; N, 4.60; F, 40.16; Cl, 12.97.

EXAMPLE 15 CF MQ C F3 /2 A 17-gram sample of diphenyl ether, 3.2 g. of aluminum chloride and 40 g. of hexafluoroisopropylideueimine were heated at 150 C. for 8 hours as per Example 1. The semisolid recovered from the autoclave (53 g.) was treated with 300 ml. of ether and filtered to remove solids. Evap oration of the ether from the filtrate gave 50 g. of residue, 22 g. of which was distilled through a short column to give 17.2 g. of product, B.P. ca. 149-162 C. (1 mm.). This material was redistilled through a spinning-band column and gave 8.0 g. of 4,4'-oxybis[a,a-bis(trifiuoromethyl)- benzylamine], also called 4,4'-bis(Z-aminohexafluoroisopropyl)diphenyl ether, B.P. 124 C. (0.2 mm.), MP. 50 52 C. This benzylamine had the UV spectrum max.

the F NMR spectrum (a singlet at +4226 c.p.s. from internal FCCl at 56.4 mc.) required by its structure. Its mass spectrum showed a parent at m./e. 500 which gives its molecular weight and a base peak at m./e. 431 (parent less CF The H NMR showed the expected A 13 pattern centered at 1-=2.6 and a NH peak at 7:796.

Analysis.Calcd. for C H ON F (500.30): C, 43.21; H, 2.42; N, 5.60. Found: C, 43.46; H, 2.48; N, 5.60. A lower boiling fraction of the distillation, 1.4 g., B.P. 117119 C. (0.2 mm.), contained, in addition to the 2:1 adduct described above, a smaller amount of 4-phen0Xya,oc-biS (trifluoromethyl)benzylamine as evidenced by its gas chromatographic retention volume (falling in between diphenyl ether and the 2:1 adduct) and an F NMR signal in the expected position of +4328 c.p.s. from internal FCC1 at 5 6.4 mc. (an unsplit singlet).

EXAMPLE 16 O sh Ha An 18 g. sample of anthracene was heated at 150 C. for 8 hours with 2.8 g. of aluminum chloride, 200 ml. of carbon disulfide and 17 g. of hexafluoroisopropylideneimine. Evaporation of the solvent gave a greenish solid. Vacuum sublimation at 120 C. (0.05 mm.) gave 15 g. of 9-(2-aminohexafluoroisopropyl)anthracene, M.P. 210 C. The H NMR (DMSO-d showed a complex aromatic absorption at T=2.23.8 (very much like the aromatic pattern of 9-methylanthracene except spread out more) and an -NH absorption at 1-=7.35 in the proper ratio. The F NMR showed a singlet at +4068 c.p.s. from int. FCCl The mass spectrum showed a molecular weight of 343 and the expected cracking pattern.

Analysis.-Calcd. for C H F N (343.27): C, 59.47; H, 3.23; F, 33.21; N, 4.08. Found: C, 59.97; H, 3.35; F, 32.60; N, 4.02.

EXAMPLE 17 or F@ (C a)2C=NH F-Q-t'J-Ntti A 50 g. sample of fluorobenzene, 11 g. of aluminum chloride and g. of hexafluoroisopropylideneimine were heated together at 250 C. for 8 hours. Filtration of the reaction mixture gave a solid which was mixed with 50 ml. of saturated sodium bicarbonate solution and extracted with ether (500 ml.) (brine and water were used to break emulsions). The ether extract was washed with sodium bicarbonate solution and with water and dried over magnesium sulfate. Concentration and distillation (spinning-band) gave 13.8 g. of 411Il01'O-u,otbiS (trifluoromethyl)benzylamine, B.P. 69 C. (10 mm.). The H NMR showed a characteristic A B pattern With halves centered at 12.12 and 2.83 (each split further) and an NH band at 77.80. The ultraviolet was characteristic of a para-disubstituted benzene A323? 266 (6:271), 259 (6 289), 257.5 (6 292), 255 (6 251), 252.5 my (6:248)

Analysis.Calcd. for C H NF (261.15): C, 41.39; H, 2.32; N, 5.37; F, 50.93. Found: C, 41.98; H, 2.44; N, 5.48; F, 51.07.

EXAMPLE 18 (aat gim A 36 g. sample of diphenylamine, 2.5 g. of aluminum chloride and 36 g. of hexafiuoroisopropylideneimine were heated together at 100 C. for 8 hours. The dark solid (64 g.) thus obtained was mixed with 5 g. of solid sodium bicarbonate and distilled through a short column. The fraction boiling at about C. (0.75 mm.), 24 g., was washed with pentane and yielded 18.6 g. of white crystals (M.P. 83-85 C.) of 4,4'-bis(Z-aminohexafluoroisopropyl)diphenylamine. The F NMR showed a singlet at +4233 c.p.s. (internal FCCl and the H NMR showed a characteristic A B pattern (1:85) with halves 1 Dimethylsulfoxide-ds.

1 1 at 72.4 and 3.0, an -NI-I absorption at 14.2 and -NH band at 78.0.

Analysis.Calcd. for C H F N (499.30): C, 43.30; H, 2.62; N, 8.42; F, 45.7. Found: C, 43.00; H, 2.60; N, 8.68; F, 44.88.

A 26 g. sample of 4-hydroxy-a,u-bis(trifiuoromethyl)- benzylamine, 2.2 g. of aluminum chloride and 20 g. of hexafluoroisopropylideneimine were heated at 200 C. for 8 hours. The recovered solid (42 g.) was combined with 50 ml. of ether and 50 ml. of pentane and filtered. The filtrate was dried over magnesium sulfate and the solvents were removed. The residue (30 g.) was vacuum sublimed at 67 C. (0.05 mm.) ll C. (0.03 mm.); a total of 16.7 g. (36%) of 2,4-bis(2-aminohexafluoroisopropyl)phenol was obtained. A center fraction, collected at 70 C. (0.05 mm.) had a M.P. of 8284 C. The H NMR spectrum (CDCl showed aromatic absorption at 'r2.03.3 and a broad peak centered at T8 and the P NMR exhibited two singlets at +4196 and 4233 c.p.s. (int. FCCl some very minor impurities present).

Analysis.-Calcd. for C H F N O (424.21): C, 33.97; H, 1.90; N, 6.61; F, 53.8. Found: C, 34.15; H, 2.21; N, 6.33; F, 53.41.

EXAMPLE 20 An 18 g. sample of diphenyl sulfide, 3 g. of aluminum chloride and 34 g .of hexafluoroisopropylideneirnine were heated at 150 C. for 8 hours. The recovered product (39 g.) was combined with g. of solid sodium bicar bonate and distilled through a short column. The fraction boiling at 173-176 C. (0.3 mm.), 19.4 g., was 4,4'-bis(2-aminohexafluoroisopropyl)diphenyl sulfide. The H NMR showed the characteristic A B pattern and an -NH absorption. The F NMR was a singlet at +4207 c.p.s. (int. FCCl Analysis.Calod. for C H F SN (516.37) C, 41.87; H, 2.35; N, 5.43; F, 44.2. Found: C, 42.08; H, 2.58; N, 5.66; F, 44.27.

EXAMPLE 21 A 34 g. sample of hexafluoroisopropylideneimine was added to 3 g. of aluminum chloride and 18 g. of bibenzyl as per Example 1 (150 C. for 8 hr.). The recovered product was combined with 5 g. of solid sodium bicarbonate and distilled through a spinning-band column. The product, 4,4-bis(2-aminohexafluoroisopropyl)bibenzyl, 8.6 g. (16%), BR 145-146 C. (1-2 mm.), was collected. A pentane-washed sample melted at 116-l17 C. The H NMR showed the characteristic A 13 pattern centered at 2.31 and 2.79 for aromatic protons, a sharp singlet at 7.04 (-CH CH and a broad singlet at 7.86 (2NH The F NMR showed a singlet at +4217 c.p.s. from int. FCCl The mass spectrum showed a molecular weight of 512 and the required fragmentation.

Analysis.Calcd. for C H N F (512.35): C, 46.88; H, 3.15; N, 5.47; F, 44.50. Found: C, 47.14; H, 3.26; N, 5.42; F, 44.68.

EXAMPLE 22 A 34 g. sample of hexafluoroisopropylideneimine was added to a mixture of 6 g. of aluminum chloride and 45 g. of bromobenzene in an autoclave. The autoclave was heated at 275 C. for 8 hr. The recovered material was filtered through a sintered-glass funnel and the solid thus obtained was mixed with 60 ml. of saturated sodium bicarbonate solution and extracted with ether. The ether extracts were washed with sodium bicarbonate solution, then with water, and dried over magnesium sulfate. Removal of the ether followed by distillation afforded 0.7 g. of 4-bromo-a,u-bis(trifluoromethyl)benzylamine, B.P. 122 C. (10 mm.), M.P. 35-36" C. The F NMR showed a singlet at +4212 c.p.s. from int. FCC13. The H NMR shows aromatic absorption at 72.4 and an -NH peak at 77.83. The mass spectrum showed a molecular weight of 322 and the required fragmentation.

Analysis.-Calcd. for C H BrF N (322.07): C, 33.56; H, 1.88; N, 4.35; F, 35.38; Br, 24.81. Found: C, 34.11; H, 2.08; N, 4.03; F, 34.44; Br, 23.79.

EXAMPLE 23 CF3 CFS l /C=NH CH3 CH CE-NH2 C F201 CF26].

A 4.8 g. sample of 4-methyl-u-trifiuoromethyl-a-chlorodifiuoromethylbenzylamine, B.P. 79 C. (0.75 mm.), was prepared from 30 g. of toluene, 18 g. of chloropentafluoroisopropylideneimine and 3 g. of aluminum chloride by heating at C. for 8 hr. as per Example 1. The reaction mixture recovered from the autoclave (46 g.) was filtered and the filtrate was distilled to isolate the product. This benzylamine had a characteristic A B pattern at r=2.6, CH absorption at 7:7.71 and an NH peak at 1-=7.9 in the H NMR. The F NMR had an A 13 (1:12) pattern at +4076 (CF;,) and +3372 c.p.s. (CF Cl) from int. FCCl at 56.4 mc.

Analysis.Calcd. for C H F NCl (273.64): C, 43.88; H, 3.32; N, 5.13; F, 34.72; Cl, 12.96. Found: C, 44.60; H, 3.48; N, 4.97; F, 34.17; Cl, 12.91.

EXAMPLE 24 A 3 g. sample of aluminum chloride was added at 78 C. to a solution of 6.4 g. of decafluoro-3-pentylideneimine in 25 g. of toluene and the mixture was heated to C. for 8 hr. The recovered product was combined with ca. 150 ml. of ether and the resulting mixture washed with sodium bicarbonate solution. The bicarbonate washings were back-extracted with additional ether. The combined ether layers were washed with water, dried over magnesium sulfate and concentrated to 25 ml. under reduced pressure, and then distilled through a spinningband column. The fraction boiling at ca. 30 C. (0.5 mm.), weighing 0.7 g. (8%), was 4-methyl-u,abis(pentafluoroethyl)benzylamine. The P NMR showed singlets at +4370 (2CF and +6601 c.p.s. (2CF from int. FCCl The H NMR showed an A B pattern at 72.4

13 and 2.85, -CH absorption at 7.63 and an NH peak at 7.85.

Analysis.-Calcd. for C H NF (357.20): C, 40.35; H, 2.54; N, 3.92; F, 53.19. Found: C, 41.14; H, 2.83; N, 3.76; F, 53.44.

The products of Examples 25 through 45, Table I, were prepared following the procedure of Example 1,

employing the reactants shown in the left and center columns in place of the corresponding reactants of Example 1.

Table II summarizes Examples 46 through 49, carried out in the manner of Example 1 but using the reactants and catalysts listed in place of the corresponding reactants and catalysts of Example 1.

n as CF3CCF3 Ham-SQ ll 37 CF3CCF3 CFa TABLE I-Continued Example N o. Polytluoroalkylideneimine HQH compound Product 0H3 011 out on NH l CFs as ora-ii-oaa moo-G HsC0-NH2 a. a

NH c1 or CF; ora-h-or; 110G HOQ-(E-Nlh a, a, in

NH CH3 CH3 CFaCl ClCFzrPJ-CFzCl (ILOMNQ mo m-b-r1m JFzCI NH CHr-CHz CF20} 41 oionr-iz-omoi on, OHQQ /CH2)-CHA(JNH3 GHQ-C M FzCl NH Qra E ma-C cm 42 era-(Lora LEO-Q HO-QC-NH: ona

a F NH 1 i CF: 43 crab-org CHsCIIzNH-Q 01130 lhNH-Q-ONH: F I]? CFa NH (1113 (1H3 CH: CH; CF: 44 CFa( 3-CFa Q C-NH1 CH2 on; em CH3 NH CaF7 45 CzF7-( 3--CaF1 OzN(OHa)a- ONQKIHMQGCNE CaFI TABLE 11 fifi Polyfluoroimine HQH compound Catalyst Product NH or; 46 CFs-%CF3 HOQ F6013 H0--b-NH,

NH 01% CFa- C 3CFa (CHah-NQ snort (CHsh-N-Q-(J-NH,

NH on; 48 org-P1 01; HO-Q HF/BF; HO-Q-b-NH,

NE on, 49 ore-h-or; (CHmN-Q znol, oH=)rN-@i1vm The novel fiuorinated benzylamines of this invention are useful as plasticizers, heat-transfer media which are stable in the presence of metal, and as monomers for the formation of polymers, for example, polyamides. The following examples illustrate the utility of the products of this invention.

EXAMPLE 50 Samples of polymethyl methacrylate were placed in three test tubes labeled A to C. To tube A was added enough hot chloroform to dissolve the polymer. T 0 tube B was added an equal part (estimated by volume) of 4- in Example 1, followed by enough hot chloroform to dissolve the one-to-one mixture. To tube C was added onehalf part of m x-bis(trifluoromethyl)benzylamine, prepared as in Example 8, followed by enough hot chloroform to dissolve the mixture. The chloroform solutions were poured onto glass plates and allowed to stand at room temperature for about one hour. Samples were scraped from the plates and compression molded at ISO-140 C. and 400 p.s.i. Sample A gave a brittle, bubbly product. Samples B and C, however, gave colorless, pliable films which could be creased without cracking, unlike the brittle hydroxy-a,u-bis(trifluoromethyl)benzylamine, prepared as films pressed from untreated polymer. This experiment EXAMPLE 51 A sample of 4-methyl-u,a-bis(trifluoromethyl)benzylamine, prepared as in Example 6, was dissolved in ether; the solution was washed with aqueous sodium bicarbonate, then with water, and dried over anhydrous magnesium sulfate. The ether solution was concentrated and distilled. Samples of the benzylamine thus obtained were sealed under vacuum in glass tubes with and without pieces of metal, as specified below. Gas chromatography analysis showed no visible decomposition of the benzylamine when heated at 200 C. for 24 hours alone or in the presence of aluminum, copper, or soft iron. This experiment illustrates the usefulness of the compounds of this invention as heat transfer media which are stable when in contact with metal.

EXAMPLE 52 A 1.0 g. sample of 54% sodium hydride suspended in mineral oil was washed three times with benzene (to remove the mineral oil) and suspended in 60 ml. of anhydrous ethylene glycol dimethyl ether (glyme). A g. sample of 4,4' oxy bis[a,a-bis(trifiuoromethyl) benzylamine], prepared as in Example 15, dissolved in 10 ml. of glyme was added dropwise at room temperature. After stirring at room temperature for 18 hours to form the sodium salt, 3.7 g. of freshly distilled adipoyl chloride was added dropwise at 0-10 C. with stirring. The gray reaction mixture was refluxed and stirred for 22 hours and then 300 ml. of water was added at 0 C.-room temperature. The resulting mixture was extracted with ether and the ether extracts were washed with saturated sodium bicarbonate solution, then with water until neutral, and dried over anhydrous magnesium sulfate. After filtration the ether was evaporated and the residue (7 g.) was dried at 60 C. (1 mm.) The solid gave a viscous melt when molten and exhibited the infrared spectrum expected for the polymer.

AnaIysis.-Calcd. {01' (C24H13N303F12) (600.30) N, 4.58; F, 37.4. Found: N, 4.59; F, 38.6.

The reaction by which polymer is formed is summarized in the equations which follow:

(IJF t ll. o-, NHCOCNHC(CHz)4 L JIFg 61 3 L A piece of aluminum foil was melt-coated at 4000 p.s.i. with the above polymer. The coated area was unaffected by concentrated hydrochloric acid while uncoated aluminum foil reacted readily with the acid and was eaten away. This example demonstrates the usefulness of the amines of this invention in the formation of polymers, and more particularly, the utility of the diamines of this invention as monomers for the formation of polyamides. Moreover, this experiment establishes, but does not limit, the utility of the polyamides thus formed.

The embodiments of the invention in which an exclu- 18 sive property or privilege is claimed are defined as follows:

1. A benzylamine having the formula C F 3Y1 Q-(-NHa) 61W wherein:

Y is fluorine, chlorine or 1-6 carbon perfiuoroalkyl,

w-chloroperfluoroalkyl or w-hydroperfiuoroalkyl;

Y is hydrogen,

fluoroalkyl, o-chloroperfluoroalkyl or w-hydroperfluoroalkyl, with the proviso that when Y is hydrogen, Y is fluorine or l-6 carbon perfluoroalkyl;

n is an integer from 1-2; and

Q is a radical formed by removal of n hydrogen atoms from an aromatic compound HQH which contains at least one aromatic ring capable of entering into Friedel-Crafts condensation reactions with alkyl halides in the presence of aluminum chloride;

said aromatic compound HQH being selected from the group consisting of monocyclic, polycyclic, and fused polycyclic compounds containing 1-3 six-membered carbocyclic aromatic rings, and polycyclic compounds containing 2 six-membered carbocyclic aroematic rings joined through a bridge selected from the group consisting of 0, -S,

ALB and {-CH R being hydro-gen, phenyl or alkyl of 1-6 carbon atoms and m being an integer from l-6; with the proviso that each acid carbocyclic aromatic ring contains 04 substituents selected from the group consisting of alkyl, perfluoroalkyl, hydroxy, alkoxy, phenoxy, alkylthio, amino, monoalkylamino, dialkylamino, cyclopentyl, cyclohexyl, halo and nitro, with each of said alkyl and alkoxy moieties containing 1-6 carbon atoms. 2. The process for the preparation of a benzylamine of claim 1 which comprises reacting an aromatic compound HQH as defined in claim 1 with a polyhaloalkylideneimine having the formula Y and Y being as defined in claim 1, under autogenous pressure, in the presence of at least 0.005 weight percent, based on the weight of said imine, of a Friedel- Crafts catalyst and in the temperature range of 0 to 300 C., the molar ratio of said imine to HQH compound being in the range of 0.25:1 to 5: 1.

3. 4,4 oxybis[a,a-bis(trifiuoromethyl benzylamine].

4. 4,4'-bis(2-aminohexafluoroisopropyl)bibenzyl.

5. 4,4-bis(Z-aminohexafluoroisopropyl)diphenylamine.

fluorine, chlorine or l-6 carbon per-.

Col. 1, line 39 "R should be Y Col. 2, line 55',

"the" should be The ,3? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,4 +6,8 l-5 Dated May 27, 1969 Inventor(s) David M. Gale It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 3, line 57,

convention" should be conventional Col. the first formula. in the equation numbered "2.", line 60,

I! H 1:10 5 should be I IC H C01. C01. 10, line 75, Col. 13, Table I,

5: line 55:

CF3 C C3 Col. 17, line ll,

Col. 18, line 32, C01. 18, line 52,

"(trifluoromethyl" and .Lttcst:

Edward M. Fletcher, Jr.

Attesting Officer "13" should be 1.3 7, line 65, "'r 2.3" should be 8, line 9, ".2 4 should be 2 "(600.30)" should be (610.50) Claim 1, "acid" should be said and Claim 3, insert a parenthesis between "benzylamine1."

SIGNED KND SEALED was 1970 WILLIAM E. soHuYLER. m. Comissioner of Pawnts 

